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Concepts in Materials Science I

StatMech Basics II

VBS/MRC Stat Mech II 0


Concepts in Materials Science I

Microcanonical Ensemble
Calculate (E, V, N )
S(E, V, N ) = kB ln
Can derive any thermodynamic potential with this
Example: Equilibrium concentration of vacancies
Example: Negative thermal expansion of polymers

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Concepts in Materials Science I

Some Useful Formulae


Several formulae come in handy when trying to count!
For large N , ln (N !) = N ln N N ...the Sterling
approximation
R x2 p
Another, useful formula e dx =
..
Dont bother if you dont follow all the mathematical
details...just make sure that you follow the logic

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Concepts in Materials Science I

Equilibrium Concentration of Vacancies


It is well known that the equilibrium concentration of
vacancies in a solid scales as eEv /kB T where Ev is the
vacancy formation energy...where does this come
from?
Logic:
1. Compute entropy for a given concentration c of
vacancies S(c)
2. Compute Helmholtz free energy A(T, c) = U T S
3. Find the value of c that minimizes A, this gives the
equilibrium concentration of c

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Concepts in Materials Science I

Equilibrium Concentration of Vacancies


Solid thought of a collection of N atomic sites
Each site may or may not be occupied
If a site is not occupied then the system has an
additional energy...the vacancy formation energy Ev
Assume now that No sites are occupied and Nv sites
are vacant
How many microstates are possible?

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Concepts in Materials Science I

Equilibrium Concentration of Vacancies


 
N! N!
= No !Nv ! , thus, S = kB ln No !Nv !

Taking c = NNv and NNo = (1 c), we get


S = N kB (c ln c + (1 c) ln (1 c))
The internal energy of the system is U = N cEv
The Helmholtz free energy
A(T, c) = U T S = N (cEv +kB T (c ln c + (1 c) ln (1 c))
A(T,c)
Taking c  1, N cEv + kB T c ln c
Equilibrium concentration c eEv /kB T

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Concepts in Materials Science I

Thermal Expansion of Polymers


Experiment: Take a piece of rubber band, and use it
to hang a weight...gently heat the rubber band...you
will see that the weight will be lifted up!
Moral: Soft polymers contract on heating! (Why?)

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Concepts in Materials Science I

Chain Model for Polymers


Think of a polymer as a chain of N links each of
length a, total length of chain L = N a under the
action of a dead load F
The chain folds up such that the
end-to-end distance is ` (no energy cost to bend bonds)

F
`
Strategy: Calculate S, and from there G...the Gibbs
free energy (Recall, system kept at constant
pressure (force) and temperature minimizes Gibbs
free energy...
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Concepts in Materials Science I

Chain Model for Polymers


To calculate the entropy, we need to find the number
of ways the chain of total length L = N a can have end
to end distance of ` = na (a length of a unit
polymer)
In a simple 1 D thinking, the chain is made of
segments that are pointing from left to right, and
those that are pointing from right to left
Let n = # segments from left to right, n = #
segments from right to left
N +n
Also, n + n = N and n n = n, or n = 2
and n = N 2n
N! N!
= (n )!(n )! =
( N +n
2 ) ( 2 )
! N n !

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Concepts in Materials Science I

Chain Model for Polymers


With a little algebra
kB
 ` `
 ` `

S = kB ln = 2 (1 L ) ln 1 L + L ln L
Since, bond-bending costs no energy, U = 0
G = U T S F ` =  
kB T ` ` ` `
2 (1 L ) ln 1 L + L ln L F`
At a given temperature T and force F , the equilibrium
value of ` is found to be (by G/` = 0 as
2F L
` e kB T
= 2F L
L 1 + e kB T
Check limits, T 0 and T !

VBS/MRC Stat Mech II 9


Concepts in Materials Science I

poly.nb
Chain Model for Polymers 1

lL
1
0.9
0.8
0.7
0.6
T kB

5 10 15 20 2 FL

There is amazingly good qualitative agreement!


Note that this effect is entirely due to entropy!

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Concepts in Materials Science I

Stock Taking..
Microcanonical Ensemble: Count states, Find Entropy,
Get Any Thermodynamic Potential
This is possible only in simple cases, since
determination of can be nontrivial
Further, we always work at constant (T, V, N ) or
(T, P, N ) and therefore look to determine A or G...
Is there a direct way to get there rather than go
through S?
Yes! The Canonical Ensemble...system kept at
constant (T, V, N )! But, first some thermodynamics...

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Concepts in Materials Science I

Helmholtz Free Energy


A system kept at constant (T, V, N ) will got to a state
of minimum Helmholtz free energy A = U T S
dA = dU T dS SdT = SdT P dV + dN
Thus,

A A A
= S, = P, =
T V,N
V T,N
N T,V

Also,

2A
CV = T
T 2

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Concepts in Materials Science I

Canonical Ensemble
Consists of a
System + a Reservoir that make up the Universe
Energy Permiable
Membrane





E + E R = EU









V + V R = VU









N + NR = NU





















System + Reservoir = Universe
System  Reservoir
The Universe is microcanonical...thus system and
VBS/MRC reservoir are at the same temperature T Stat Mech II 13
Concepts in Materials Science I

Canonical Ensemble
What is the probability that the system has energy E?
(E,V,N )R (EU E,VR ,NR )
EAPP...P (E) = U (EU ,NU ,VU )
SR (EU E,VR ,NR )
Look at R closely.. R = e kB

S
SR (EU E, VR , NR ) SR (EU , VR , NR ) ( )E =
| {z } | E {z }
0
SR
1/T
0 E SR k ET
SR T, Thus, R e k e B

SR
e k 1
Since, U = const, P (E) (E, V, N )eE , = kB T
This is it!

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Concepts in Materials Science I

Canonical Ensemble
The probability of a microstate with energy E of the
system is proportional to eE
We can fix the constant of proportionality...Z =
R E
R E(C)
0 (E, V, N )e = Ce dC...note that we can
convert the integral over energy to integral over all
configurations (all phase space in classical mechanics)
and thus avoid counting of states!
R E(C)
Z = Ce dC is called the Partition Function and
has all thermodynamics information!
eE(C)
P (C) = Z
How does Z give thermodynamics?

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Concepts in Materials Science I

Canonical Ensemble
Energy of our system fluctuates, but the mean
energy E is the internal energy U ...That is
1
R
U = E = Z C EeE(C) dC
A bit of algebra get: U =
ln Z

U 2F
Note now that T= T T 2 ,
a bit more algebra later :
A = kB T ln Z...THIS IS THE FORMULA OF
STATMECH
Calculate partition function Z and...you are home!
Canonical advantage: Dont have to count
states...every state Cis possible with probability
eE(C)

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Concepts in Materials Science I

StatMech So Far
Microcanonical Logic: Count states, Calculate entropy,
Thermodynamic functions
Canonical (T, V, N ) logic: Any microstate in this
ensemble has probability proportional to
eE ...Calculate the partition function Z and
A = kB T ln Z...everything else follows
Canonical Ensemble Example: Ideal Gas
Canonical Ensemble Example: Harmonic Oscillator
Canonical Ensemble Example: Classical Solid

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Concepts in Materials Science I

Ideal Gas
N non-interacting atoms occupying a region of volume
V at temperature T (Recall, satisfies
P V = N kB T ...where does this come from?)
Main idea...in canonical ensemble any microstate C is
possible with probability eE(C)
Microstate is
(r 1 , ..., r N , p1 , ..., pN )dr 1 ...dr N dp1 ...dpN .....the energy
PN pi pi
associated is i=1 2m
Partition function
R R R R
P
N p i p i

1
Z = ~3N N ! V dr 1 ... V dr N dp1 ... dpN e i=1 2m

Simplifies to
 N  3N
VN
R p2
V N

2m 2
Z = ~3N N ! e 2m dp = ~3N N !
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Concepts in Materials Science I

Ideal Gas
Internal energy U = E =
ln Z
= 32 N kB T !
Now, with   
3N 2m
A = kB T N ln V N ln N + N + 2 ln ~2 , and
A N kB T
P = V , we get P = V ...Shri. Bolye rises from
microscopics!
The mean energy is U ...but what about standard
deviation? This is
2 ln Z
U = (E E) = 2 = 32 N kB
2 2 2 T 2 ...thus

U
U 1 0 as N ! Thermodynamic limit,
N
and why we see very reproducible things in
experiments with no affect of particular microstates
etc...think of the copper puzzle...it is resolved!
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Concepts in Materials Science I

A Single Classical Harmonic Oscillator


What is internal energy and specific heat? (Note,
p2 m 2 2
H= 2m + 2 x )
Microstate (x, p) is possible with probability eE
Partition function Z= 
p 2 m 2 2 q q
1
R R + x 1 2 2m 2
~ dx dp e 2m 2
= ~ 2
m = ~

U = E =
ln Z
= kB T ! Looks familiar!
Specific heat C = kB ...also familiar!

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Concepts in Materials Science I

A Single Classical Harmonic Oscillator (3D)


What is internal energy and specific heat? (Note,
pp m2
H = 2m + 2 r r)
Microstate (r, p) is possible with probability eE
R

p p m 2
2m + 2 r r

Partition function Z = ~13 drdp e =
q 3 q 3  3
1 2 2m 2
~ 3 2
m = ~

U = E =
ln Z
= 3kB T ! Looks familiar!
Specific heat C = 3kB ...also familiar!

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Concepts in Materials Science I

Classical Solid
The solid (N ) atoms may be thought of as a collection
of 3N oscillators (phonons) with Hamiltonian (roughly) 
P P k P k mk2
H(A1 , ..., AN , P 1 , ..., P N ) = k 2m + 2 Ak A k ,
where k (total of N ) is the wavevector of the phonon
Since these are independent oscillators, we have
Q  2 3
Z = k ~k
P   P
U =
ln Z
= k 3 ln 2
~k = k 3kB T =
3N kB T
C = 3N kB , but hey, thats Dulong-Petit!

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Concepts in Materials Science I

Just one more thing!


U
How do we get specific heat CV ? Well, CV = T
U 2 ln Z
CV = T = kB 2 U
= 2
kB 2
2 ln Z 1
But, 2 = U 2 , or CV = kB T 2 U 2!

Turns out that this is a key physical


result...fluctuations at equilibrium are a measure of
how system resists change of equilibrium! Related to
the more general Fluctuation-Dissipation Theorem

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Concepts in Materials Science I

Summary
Canonical Logic: Calculate partition function...obtain
free energy...go home!
We have seen how StatMech helps understand
material properties...from equilibrium concentration of
vacancies, to polymers, to ideal gases etc!
Next we shall look at Quantum Statistical
Mechanics...essentially same ideas, but counting will
be different respecting type of particles...Bosons or
fermions

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